JPH05178960A - Epoxy resin and composition containing same - Google Patents
Epoxy resin and composition containing sameInfo
- Publication number
- JPH05178960A JPH05178960A JP35817191A JP35817191A JPH05178960A JP H05178960 A JPH05178960 A JP H05178960A JP 35817191 A JP35817191 A JP 35817191A JP 35817191 A JP35817191 A JP 35817191A JP H05178960 A JPH05178960 A JP H05178960A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- bisphenol
- group
- phenolic hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なエポキシ樹脂及
びその組成物に係わり、更に詳しくは、硬化物の耐熱
性、耐水性に優れたエポキシ樹脂及びその組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy resin and a composition thereof, and more particularly to an epoxy resin excellent in heat resistance and water resistance of a cured product and a composition thereof.
【０００２】[0002]
【従来の技術】エポキシ樹脂は、硬化物の機械的強度、
耐薬品性、接着性等に優れた特性を有し、電気・電子用
材料、塗料、複合材料等の広い分野で使用されている。
しかし、特に粉体塗料、電気用積層板、電線ワニス等の
用途に、最も一般的に用いられているビスフェノールＡ
型固形エポキシ樹脂を用いた樹脂組成物は、硬化物の耐
熱性が十分ではないという問題がある。2. Description of the Related Art Epoxy resins are the mechanical strength of cured products.
It has excellent chemical resistance and adhesive properties, and is used in a wide range of fields such as electrical and electronic materials, paints, and composite materials.
However, bisphenol A is most commonly used for powder coatings, electrical laminates, wire varnishes, etc.
The resin composition using the solid epoxy resin has a problem that the heat resistance of the cured product is not sufficient.
【０００３】一方、ビスフェノールＡ型固形エポキシ樹
脂の耐熱性向上の目的でオルソクレゾールノボラック型
エポキシ樹脂等の多官能エポキシ樹脂を添加した場合、
耐熱性は向上するものの、耐水性が悪化するという欠点
があり、耐熱性と耐水性の両方に優れた硬化物を与える
エポキシ樹脂及びその組成物が望まれていた。On the other hand, when a polyfunctional epoxy resin such as orthocresol novolac type epoxy resin is added for the purpose of improving the heat resistance of the bisphenol A type solid epoxy resin,
Although the heat resistance is improved, there is a drawback that the water resistance is deteriorated, and thus an epoxy resin and a composition thereof which give a cured product excellent in both heat resistance and water resistance have been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、硬化物の耐
熱性、耐水性に優れたエポキシ樹脂及びその組成物を提
供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy resin having excellent heat resistance and water resistance of a cured product and a composition thereof.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を解決するため鋭意研究を重ねた結果、エポキシ樹脂中
にフルオレン骨格を導入することにより、硬化物の耐熱
性、耐水性に優れたエポキシ樹脂組成物が得られること
を見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned object, the present inventors have introduced a fluorene skeleton into an epoxy resin, and thereby have excellent heat resistance and water resistance of a cured product. It was found that an epoxy resin composition was obtained, and the present invention was completed.
【０００６】すなわち本発明は、下記一般式（１）That is, the present invention provides the following general formula (1)
【化２】 で表されるエポキシ樹脂である。[Chemical 2] Is an epoxy resin represented by.
【０００７】また、本発明は、分子中に２個のフェノー
ル性水酸基を含有するフェノール類と、分子中に２個の
エポキシ基を含有するエポキシ樹脂との付加反応により
合成され、かつ、上記フェノール類の５０重量％以上が
９，９’−ビス（４−ヒドロキシフェニル）フルオレン
であり、上記エポキシ樹脂の５０重量％以上がビスフェ
ノールＡ型エポキシ樹脂であり、上記フェノール性水酸
基とエポキシ基のモル比が０．２：１から０．９：１で
あるエポキシ樹脂を必須の成分として含有する樹脂組成
物である。Further, the present invention is synthesized by an addition reaction of a phenol having two phenolic hydroxyl groups in the molecule with an epoxy resin having two epoxy groups in the molecule, and the above-mentioned phenol. 50% by weight or more of the class is 9,9'-bis (4-hydroxyphenyl) fluorene, 50% by weight or more of the epoxy resin is bisphenol A type epoxy resin, and the molar ratio of the phenolic hydroxyl group to the epoxy group is Is a resin composition containing an epoxy resin of 0.2: 1 to 0.9: 1 as an essential component.
【０００８】本発明のエポキシ樹脂は、過剰のビスフェ
ノールＡ型エポキシ樹脂と９，９’−ビス（４−ヒドロ
キシフェニル）フルオレンとの付加反応により合成でき
る。The epoxy resin of the present invention can be synthesized by an addition reaction between an excess bisphenol A type epoxy resin and 9,9'-bis (4-hydroxyphenyl) fluorene.
【０００９】本発明のエポキシ樹脂は、その製造時にお
いて、工業的有用性、生産性を考慮して上記９，９’−
ビス（４−ヒドロキシフェニル）フルオレン以外の分子
中に２個のフェノール性水酸基を含有するフェノール類
と、上記ビスフェノールＡ型エポキシ樹脂以外の分子中
に２個のエポキシ基を含有するエポキシ樹脂を併用し、
混合系のエポキシ樹脂組成物として製造することもでき
る。その際、組成物は全フェノール類の５０重量％以上
が９，９’−ビス（４−ヒドロキシフェニル）フルオレ
ンでなければならない。このようなフルオレン骨格を導
入することにより、耐熱性、耐水性に優れた樹脂とする
ことができる。The epoxy resin of the present invention has the above-mentioned 9,9'-in consideration of industrial usefulness and productivity during its production.
Phenols containing two phenolic hydroxyl groups in a molecule other than bis (4-hydroxyphenyl) fluorene and an epoxy resin containing two epoxy groups in a molecule other than the above bisphenol A type epoxy resin are used in combination. ,
It can also be manufactured as a mixed epoxy resin composition. At that time, the composition must be such that 50% by weight or more of the total phenols is 9,9′-bis (4-hydroxyphenyl) fluorene. By introducing such a fluorene skeleton, a resin having excellent heat resistance and water resistance can be obtained.
【００１０】９，９’−ビス（４−ヒドロキシフェニ
ル）フルオレン以外のフェノール類としては、ハイドロ
キノン、レゾルシン、ビスフェノールＡ、ビスフェノー
ルＦ、ビスフェノールＳ等が挙げられる。Examples of phenols other than 9,9'-bis (4-hydroxyphenyl) fluorene include hydroquinone, resorcin, bisphenol A, bisphenol F and bisphenol S.
【００１１】また、本発明のエポキシ樹脂組成物の原料
として用いるエポキシ樹脂は、５０重量％以上がビスフ
ェノールＡ型エポキシ樹脂でなければならない。ビスフ
ェノールＡ型エポキシ樹脂以外のエポキシ樹脂原料とし
ては、ビスフェノールＦ、ビスフェノールＳ、レゾルシ
ン、エチレングリコール、プロピレングリコール、１，
４−ブタンジオール、１，６−ヘキサンジオール等とエ
ピクロルヒドリンより合成されるジグリシジルエーテル
類を１種又は２種以上を用いることができる。The epoxy resin used as a raw material for the epoxy resin composition of the present invention must have a bisphenol A type epoxy resin content of 50% by weight or more. As epoxy resin raw materials other than bisphenol A type epoxy resin, bisphenol F, bisphenol S, resorcin, ethylene glycol, propylene glycol, 1,
One or more diglycidyl ethers synthesized from 4-butanediol, 1,6-hexanediol and the like and epichlorohydrin can be used.
【００１２】また、本発明のエポキシ樹脂及び組成物
は、上記フェノール類とエポキシ樹脂の付加反応で合成
されるものであるが、原料中のフェノール性水酸基とエ
ポキシ基のモル比は０．２：１から０．９：１の範囲に
限定される。この理由は、モル比０．２以下では、フル
オレン骨格導入の効果が十分ではなく、モル比０．９以
上では、合成されるエポキシ樹脂組成物の軟化点が高く
加工性に劣るものとなるためである。フルオレン骨格導
入の効果と加工性のバランスを取るためには、原料中の
フェノール性水酸基とエポキシ基のモル比は０．３：１
から０．８：１の範囲であることがより望ましい。The epoxy resin and composition of the present invention are synthesized by the addition reaction of the above-mentioned phenols and epoxy resin, and the molar ratio of the phenolic hydroxyl group to the epoxy group in the raw material is 0.2: Limited to the range 1 to 0.9: 1. The reason is that when the molar ratio is 0.2 or less, the effect of introducing the fluorene skeleton is not sufficient, and when the molar ratio is 0.9 or more, the epoxy resin composition to be synthesized has a high softening point and poor processability. Is. In order to balance the effect of introducing the fluorene skeleton and the processability, the molar ratio of the phenolic hydroxyl group to the epoxy group in the raw material is 0.3: 1.
More preferably, the range is from 0.8 to 0.8: 1.
【００１３】本発明のエポキシ樹脂及び組成物は、エポ
キシ樹脂硬化剤を配合することにより、耐熱性、耐水性
に優れた硬化物が得られる樹脂組成物とすることができ
る。エポキシ樹脂硬化剤は、エポキシ樹脂の硬化剤とし
て公知であれば特に限定されるものではないが、例えば
無水フタル酸、無水トリメリット酸、無水ピロメリット
酸、３，３’，４，４’−ベンゾフェノンテトラカルボ
ン酸二無水物等の酸無水物や、フェニレンジアミン、ジ
アミノジフェニルメタン、ジアミノジフェニルスルホン
等の芳香族アミン類や、フェノールノボラック、オルソ
クレゾールノボラック、フロログリシノール等のフェノ
ール類等が挙げられる。The epoxy resin and composition of the present invention can be made into a resin composition by adding an epoxy resin curing agent to obtain a cured product excellent in heat resistance and water resistance. The epoxy resin curing agent is not particularly limited as long as it is known as a curing agent for epoxy resins, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′-. Examples thereof include acid anhydrides such as benzophenone tetracarboxylic acid dianhydride, aromatic amines such as phenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone, and phenols such as phenol novolac, orthocresol novolac and phloroglicinol.
【００１４】また、本発明の樹脂及び組成物は、上記エ
ポキシ樹脂及びエポキシ樹脂硬化剤の他、充填材、顔
料、硬化促進剤、カップリング剤、溶剤等の成分を適宜
使用してもよい。In addition to the above epoxy resin and epoxy resin curing agent, the resin and composition of the present invention may appropriately contain components such as filler, pigment, curing accelerator, coupling agent and solvent.
【００１５】[0015]
【実施例】以下、本発明を実施例に基づいてより具体的
に説明する。 合成例１ １リットルフラスコ中に９，９’−ビス（４−ヒドロキ
シフェニル）フルオレン１４６ｇとビスフェノールＡ型
液状エポキシ樹脂（東都化成（株）製商品名ＹＤ−１２
８、エポキシ当量１８６ｇ／ｅｑ）３５４ｇとを仕込
み、１５０℃で溶融混合させた。このときのフェノール
性水酸基とエポキシ基のモル比は０．４３：１であっ
た。その後、トリフェニルホスフィン０．０７３ｇを添
加し、１５０℃で４時間撹拌を続けて付加反応を完結さ
せ、エポキシ当量４４４ｇ／ｅｑのフルオレン骨格含有
エポキシ樹脂組成物を得た。図１にＩＲスペクトル図を
示す。EXAMPLES The present invention will be described more specifically below based on examples. Synthesis Example 1 146 g of 9,9'-bis (4-hydroxyphenyl) fluorene and bisphenol A type liquid epoxy resin (trade name YD-12 manufactured by Toto Kasei Co., Ltd.) in a 1-liter flask.
8 and epoxy equivalent 186 g / eq) 354g were prepared and melt-mixed at 150 degreeC. At this time, the molar ratio of the phenolic hydroxyl group and the epoxy group was 0.43: 1. Thereafter, 0.073 g of triphenylphosphine was added, and stirring was continued at 150 ° C. for 4 hours to complete the addition reaction to obtain a fluorene skeleton-containing epoxy resin composition having an epoxy equivalent of 444 g / eq. The IR spectrum is shown in FIG.
【００１６】合成例２ １リットルフラスコ中に９，９’−ビス（４−ヒドロキ
シフェニル）フルオレン１６８ｇとビスフェノールＡ型
液状エポキシ樹脂（東都化成（株）製商品名ＹＤ−１２
８、エポキシ当量１８６ｇ／ｅｑ）３３２ｇとを仕込
み、１５０℃で溶融混合させた。このときのフェノール
性水酸基とエポキシ基のモル比は０．５３：１であっ
た。その後、トリフェニルホスフィン０．０８４ｇを添
加し、１５０℃で４時間撹拌を続け、付加反応を完結さ
せ、エポキシ当量６３０ｇ／ｅｑのフルオレン骨格含有
エポキシ樹脂組成物を得た。Synthetic Example 2 168 g of 9,9'-bis (4-hydroxyphenyl) fluorene and a bisphenol A type liquid epoxy resin (trade name YD-12 manufactured by Tohto Kasei Co., Ltd.) were placed in a 1-liter flask.
8 and 332 g of epoxy equivalent 186 g / eq) were charged and melt-mixed at 150 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 0.53: 1. After that, 0.084 g of triphenylphosphine was added, and stirring was continued at 150 ° C. for 4 hours to complete the addition reaction to obtain a fluorene skeleton-containing epoxy resin composition having an epoxy equivalent of 630 g / eq.
【００１７】合成例３ １リットルフラスコ中に、９，９’−ビス（４−ヒドロ
キシフェニル）フルオレン１９３ｇとビスフェノールＡ
型液状エポキシ樹脂（東都化成（株）製商品名ＹＤ−１
２８、エポキシ当量１８６ｇ／ｅｑ）３０７ｇとを仕込
み、１５０℃で溶融混合させた。このときのフェノール
性水酸基とエポキシ基のモル比は０．６６：１であっ
た。その後、トリフェニルホスフィン０．０９６ｇを添
加し、１５０℃で４時間撹拌を続け、付加反応を完結さ
せ、エポキシ当量９４９ｇ／ｅｑのフルオレン骨格含有
エポキシ樹脂組成物を得た。Synthesis Example 3 193 g of 9,9'-bis (4-hydroxyphenyl) fluorene and bisphenol A were placed in a 1-liter flask.
Type liquid epoxy resin (trade name YD-1 manufactured by Tohto Kasei Co., Ltd.)
28 and an epoxy equivalent of 186 g / eq) of 307 g were charged and melt-mixed at 150 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 0.66: 1. Thereafter, 0.096 g of triphenylphosphine was added, and stirring was continued at 150 ° C. for 4 hours to complete the addition reaction to obtain a fluorene skeleton-containing epoxy resin composition having an epoxy equivalent of 949 g / eq.
【００１８】実施例１ 合成例１の方法で合成したエポキシ樹脂組成物（以下エ
ポキシ樹脂１と記す）１０ｇ、硬化剤として３，３’，
４，４’−ベンゾフェノンテトラカルボン酸二無水物
２．９ｇ、硬化促進剤として２−エチル−４−メチルイ
ミダゾール０．０５ｇを１９．４ｇのジメチルホルムア
ミドに溶解させ、１０ｃｍ×１０ｃｍガラスクロスに含
浸させ、オーブン中１５０℃で２時間乾燥してジメチル
ホルムアミドを除去した後、２００℃で２時間硬化さ
せ、硬化物を得た。得られた硬化物から１０ｃｍ×５ｃ
ｍの試験片を切り出し、沸騰水中に２４時間投入し、投
入前後の重量を測定、その後試験片を７００℃の電気炉
中で有機分を除き、ガラスクロスの重量を測定すること
により、硬化物の吸水率を求めた。また、硬化物のガラ
ス転移温度をＤＳＣにより測定した。結果を表１に示
す。Example 1 10 g of an epoxy resin composition (hereinafter referred to as epoxy resin 1) synthesized by the method of Synthesis Example 1, 3,3 'as a curing agent,
2.9 g of 4,4′-benzophenone tetracarboxylic acid dianhydride and 0.05 g of 2-ethyl-4-methylimidazole as a curing accelerator were dissolved in 19.4 g of dimethylformamide and impregnated in a 10 cm × 10 cm glass cloth. After being dried in an oven at 150 ° C. for 2 hours to remove dimethylformamide, it was cured at 200 ° C. for 2 hours to obtain a cured product. 10 cm x 5 c from the obtained cured product
A test piece of m was cut out, put in boiling water for 24 hours, the weight before and after the addition was measured, and then the test piece was removed of organic matter in an electric furnace at 700 ° C., and the weight of the glass cloth was measured to obtain a cured product. Was calculated. Further, the glass transition temperature of the cured product was measured by DSC. The results are shown in Table 1.
【００１９】実施例２ エポキシ樹脂として合成例２の方法で合成したエポキシ
樹脂組成物（以下エポキシ樹脂２と記す）１０ｇ、硬化
剤として３，３’，４，４’−ベンゾフェノンテトラカ
ルボン酸二無水物２．０４ｇを用いたほかは実施例１と
同様の方法で硬化物の吸水率とガラス転移温度を求め
た。結果を表１に示す。Example 2 10 g of an epoxy resin composition (hereinafter referred to as epoxy resin 2) synthesized by the method of Synthesis Example 2 as an epoxy resin, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as a curing agent. The water absorption and the glass transition temperature of the cured product were determined by the same method as in Example 1 except that 2.04 g of the product was used. The results are shown in Table 1.
【００２０】実施例３ エポキシ樹脂として合成例３の方法で合成したエポキシ
樹脂組成物（以下エポキシ樹脂２と記す）１０ｇ、硬化
剤として３，３’，４，４’−ベンゾフェノンテトラカ
ルボン酸二無水物１．３６ｇを用いたほかは実施例１と
同様の方法で硬化物の吸水率とガラス転移温度を求め
た。結果を表１に示す。Example 3 10 g of an epoxy resin composition (hereinafter referred to as epoxy resin 2) synthesized by the method of Synthesis Example 3 as an epoxy resin, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as a curing agent. The water absorption and the glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 1.36 g of the product was used. The results are shown in Table 1.
【００２１】比較例１ エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂
（東都化成（株）製商品名ＹＤ−０１４、エポキシ当量
９７３ｇ／ｅｑ）１０ｇ、硬化剤として３，３’，４，
４’−ベンゾフェノンテトラカルボン酸二無水物１．３
３ｇを用いたほかは実施例１と同様の方法で硬化物の吸
水率とガラス転移温度を求めた。結果を表１に示す。Comparative Example 1 10 g of a bisphenol A type epoxy resin (trade name: YD-014 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 973 g / eq) as an epoxy resin and 3,3 ', 4 as a curing agent.
4'-benzophenone tetracarboxylic acid dianhydride 1.3
The water absorption and the glass transition temperature of the cured product were determined by the same method as in Example 1 except that 3 g was used. The results are shown in Table 1.
【００２２】比較例２ エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂
（東都化成（株）製商品名ＹＤ−０１４、エポキシ当量
９７３ｇ／ｅｑ）８．５ｇ、及びオルソクレゾールノボ
ラック型エポキシ樹脂（東都化成（株）製、商品名ＹＤ
ＣＮ−７０４、エポキシ当量２１１ｇ／ｅｑ）１．５
ｇ、硬化剤として３，３’，４，４’−ベンゾフェノン
テトラカルボン酸二無水物２．０４ｇを用いたほかは実
施例１と同様の方法で硬化物の吸水率とガラス転移温度
を求めた。結果を表１に示す。Comparative Example 2 As an epoxy resin, bisphenol A type epoxy resin (trade name YD-014 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 973 g / eq) 8.5 g, and orthocresol novolac type epoxy resin (Tohto Kasei Co., Ltd.) Made, product name YD
CN-704, epoxy equivalent 211g / eq) 1.5
g, and the water absorption rate and glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 2.04 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was used as the curing agent. .. The results are shown in Table 1.
【００２３】比較例３ エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂
（東都化成（株）製商品名ＹＤ−０１４、エポキシ当量
９７３ｇ／ｅｑ）７．０ｇ、及びオルソクレゾールノボ
ラック型エポキシ樹脂（東都化成（株）製、商品名ＹＤ
ＣＮ−７０４、エポキシ当量２１１ｇ／ｅｑ）３．０
ｇ、硬化剤として３，３’，４，４’−ベンゾフェノン
テトラカルボン酸二無水物２．７６ｇを用いたほかは実
施例１と同様の方法で硬化物の吸水率とガラス転移温度
を求めた。結果を表１に示す。Comparative Example 3 As an epoxy resin, 7.0 g of a bisphenol A type epoxy resin (trade name YD-014 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 973 g / eq), and an orthocresol novolak type epoxy resin (Toto Kasei Co., Ltd.). Made, product name YD
CN-704, epoxy equivalent 211g / eq) 3.0
g, and the water absorption and the glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 2.76 g was used as the curing agent. .. The results are shown in Table 1.
【００２４】比較例４ エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂
（東都化成（株）製商品名ＹＤ−０１４、エポキシ当量
９７３ｇ／ｅｑ）５．５ｇ、及びオルソクレゾールノボ
ラック型エポキシ樹脂（東都化成（株）製、商品名ＹＤ
ＣＮ−７０４、エポキシ当量２１１ｇ／ｅｑ）４．５
ｇ、硬化剤として３，３’，４，４’−ベンゾフェノン
テトラカルボン酸二無水物３．４８ｇを用いたほかは実
施例と同様の方法で硬化物の吸水率とガラス転移温度を
求めた。結果を表１に示す。Comparative Example 4 As an epoxy resin, bisphenol A type epoxy resin (trade name YD-014 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 973 g / eq) 5.5 g, and orthocresol novolac type epoxy resin (Tohto Kasei Co., Ltd.) Made, product name YD
CN-704, epoxy equivalent 211g / eq) 4.5
g, and the water absorption and the glass transition temperature of the cured product were determined by the same method as in Example except that 3.48 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was used as the curing agent. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】上記表１に示されるように、本発明のエポ
キシ樹脂組成物を原料とする組成物は、ビスフェノール
Ａ型固形エポキシ樹脂とオルソクレゾールノボラック型
エポキシ樹脂を原料とするエポキシ樹脂組成物に比較
し、同等の吸水率ではるかに高いガラス転移温度を持つ
か、又は吸水率、ガラス転移温度ともに優れた硬化物を
与える。As shown in Table 1 above, the composition using the epoxy resin composition of the present invention as the raw material is compared with the epoxy resin composition using the bisphenol A type solid epoxy resin and the orthocresol novolac type epoxy resin as the raw materials. However, it has a much higher glass transition temperature at the same water absorption rate, or gives a cured product having excellent water absorption rate and glass transition temperature.
【００２７】[0027]
【発明の効果】本発明のエポキシ樹脂組成物及びこのエ
ポキシ樹脂組成物を含有する樹脂組成物は、吸水率が小
さく、ガラス転移温度の極めて高い硬化物を与えるもの
であり、特に塗料、電気用積層板、電線ワニス等の用途
に使用するエポキシ樹脂及び樹脂組成物として有用であ
る。INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention and the resin composition containing this epoxy resin composition give a cured product having a low water absorption rate and an extremely high glass transition temperature, and are particularly useful for paints and electrical applications. It is useful as an epoxy resin and a resin composition used for applications such as laminates and electric wire varnishes.
【図１】図１は合成例１で得られたエポキシ樹脂のＩＲ
スペクトル図である。FIG. 1 is the IR of the epoxy resin obtained in Synthesis Example 1.
It is a spectrum figure.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 隆介 神奈川県横浜市磯子区洋光台５−６−16− 504 (72)発明者 石原 一男 東京都江戸川区東葛西３−17−14、東都化 成株式会社中央研究所内 (72)発明者 中西 宏 東京都江戸川区東葛西３−17−14、東都化 成株式会社中央研究所内 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Ryusuke Hayashi 5-6-16-504 Yokodai, Isogo-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Kazuo Ishihara 3-17-14, Higashikasai, Edogawa-ku, Tokyo, Tohto Kasei Central Research Institute Co., Ltd. (72) Inventor Hiroshi Nakanishi 3-17-14 Higashikasai, Edogawa-ku, Tokyo, Toto Kasei Co., Ltd. Central Research Laboratories
Claims (2)
有するフェノール類と、分子中に２個のエポキシ基を含
有するエポキシ樹脂との付加反応により合成され、か
つ、上記フェノール類の５０重量％以上が９，９’−ビ
ス（４−ヒドロキシフェニル）フルオレンであり、上記
エポキシ樹脂の５０重量％以上がビスフェノールＡ型エ
ポキシ樹脂であり、上記フェノール性水酸基とエポキシ
基のモル比が０．２：１から０．９：１であるエポキシ
樹脂を必須の成分として含有することを特徴とするエポ
キシ樹脂組成物。2. A phenol which has two phenolic hydroxyl groups in the molecule and an epoxy resin which has two epoxy groups in the molecule are synthesized by an addition reaction, and 50 weight% of the above phenols. % Or more is 9,9′-bis (4-hydroxyphenyl) fluorene, 50% by weight or more of the epoxy resin is bisphenol A type epoxy resin, and the molar ratio of the phenolic hydroxyl group to the epoxy group is 0.2. An epoxy resin composition comprising an epoxy resin of 1 to 0.9: 1 as an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35817191A JP3287594B2 (en) | 1991-12-27 | 1991-12-27 | Epoxy resin and composition thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35817191A JP3287594B2 (en) | 1991-12-27 | 1991-12-27 | Epoxy resin and composition thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05178960A true JPH05178960A (en) | 1993-07-20 |
| JP3287594B2 JP3287594B2 (en) | 2002-06-04 |
Family
ID=18457913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35817191A Expired - Fee Related JP3287594B2 (en) | 1991-12-27 | 1991-12-27 | Epoxy resin and composition thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3287594B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073122A (en) * | 1993-06-17 | 1995-01-06 | Nippon Steel Chem Co Ltd | Thermoplastic resin composition, cured material thereof and color filter material |
| WO2000039188A1 (en) * | 1998-12-25 | 2000-07-06 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
| JP2004339499A (en) * | 2003-04-22 | 2004-12-02 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2008255309A (en) * | 2007-03-13 | 2008-10-23 | Osaka Gas Co Ltd | Epoxy resin composition and cured product thereof |
| JP2010111876A (en) * | 2003-04-22 | 2010-05-20 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2010126694A (en) * | 2008-11-28 | 2010-06-10 | Nagase Chemtex Corp | Condensed ring structure-containing phenoxy resin |
| JP2012177038A (en) * | 2011-02-25 | 2012-09-13 | Nippon Steel Chem Co Ltd | Epoxy resin composition |
| US20140203190A1 (en) * | 2012-08-22 | 2014-07-24 | Empire Technology Development Llc | Optically active epoxy |
| KR20150101932A (en) * | 2014-02-27 | 2015-09-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product thereof |
| JP2015178592A (en) * | 2014-02-27 | 2015-10-08 | 新日鉄住金化学株式会社 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product |
| WO2020111476A1 (en) * | 2018-11-28 | 2020-06-04 | 주식회사 케이씨씨 | Powder paint composition |
| CN112778702A (en) * | 2020-12-30 | 2021-05-11 | 广东盈骅新材料科技有限公司 | Epoxy resin composite material and laminated board as well as preparation method and application thereof |
-
1991
- 1991-12-27 JP JP35817191A patent/JP3287594B2/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073122A (en) * | 1993-06-17 | 1995-01-06 | Nippon Steel Chem Co Ltd | Thermoplastic resin composition, cured material thereof and color filter material |
| WO2000039188A1 (en) * | 1998-12-25 | 2000-07-06 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
| US6620510B1 (en) | 1998-12-25 | 2003-09-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
| JP2013010971A (en) * | 2003-04-22 | 2013-01-17 | Osaka Gas Co Ltd | Fluorene based composition and molded product of the same |
| JP2010111876A (en) * | 2003-04-22 | 2010-05-20 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2012041561A (en) * | 2003-04-22 | 2012-03-01 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2012082427A (en) * | 2003-04-22 | 2012-04-26 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2004339499A (en) * | 2003-04-22 | 2004-12-02 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2014040615A (en) * | 2003-04-22 | 2014-03-06 | Osaka Gas Co Ltd | Fluorene-based composition and molded product of the same |
| JP2008255309A (en) * | 2007-03-13 | 2008-10-23 | Osaka Gas Co Ltd | Epoxy resin composition and cured product thereof |
| JP2010126694A (en) * | 2008-11-28 | 2010-06-10 | Nagase Chemtex Corp | Condensed ring structure-containing phenoxy resin |
| JP2012177038A (en) * | 2011-02-25 | 2012-09-13 | Nippon Steel Chem Co Ltd | Epoxy resin composition |
| US20140203190A1 (en) * | 2012-08-22 | 2014-07-24 | Empire Technology Development Llc | Optically active epoxy |
| US9376614B2 (en) * | 2012-08-22 | 2016-06-28 | Empire Technology Development Llc | Optically active epoxy |
| KR20150101932A (en) * | 2014-02-27 | 2015-09-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product thereof |
| JP2015178592A (en) * | 2014-02-27 | 2015-10-08 | 新日鉄住金化学株式会社 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product |
| WO2020111476A1 (en) * | 2018-11-28 | 2020-06-04 | 주식회사 케이씨씨 | Powder paint composition |
| KR20200063920A (en) * | 2018-11-28 | 2020-06-05 | 주식회사 케이씨씨 | Powder coating composition |
| CN112778702A (en) * | 2020-12-30 | 2021-05-11 | 广东盈骅新材料科技有限公司 | Epoxy resin composite material and laminated board as well as preparation method and application thereof |
| CN112778702B (en) * | 2020-12-30 | 2023-03-07 | 广东盈骅新材料科技有限公司 | Epoxy resin composite material and laminated board as well as preparation method and application thereof |
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